JPH0246676B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a plating solution for electroplating zinc-nickel alloys, and more specifically,
Improved chloride type and its variant chloride-sulfate mixed type containing novel additives to improve the compositional uniformity of alloy plating coatings over a wide current density range. This invention relates to an aqueous acidic zinc/nickel alloy electroplating solution. BACKGROUND ART Decorative or functional zinc-nickel alloy coatings are applied to iron or steel for the purpose of overlaying to improve corrosion resistance, improve appearance, and/or enable refinishing to restore the dimensions of worn areas. Plating solutions containing a certain amount of zinc and nickel ions have been used and proposed for electrodeposition on various substrates such as steel (Japanese Patent Laid-Open No. 58-34189).
No. etc.). Such zinc-nickel alloy electroplating solutions are widely used for industrial or functional plating of strips, conduits, wires, rods, tubes, couplings, etc. Problems to be Solved by the Invention Many improvements have been made in the past to achieve the fine particle size of the plating film necessary to obtain a desirable semi-gloss appearance and better adhesion. A related problem remains that the nickel content of zinc-nickel alloys tends to vary widely due to different current densities depending on the part of the article being plated. This variation in the nickel content of electroplated coatings is
This has an adverse effect on the subsequent treatment with a conventional chromate solution for chromating the plated article in order to further improve its corrosion resistance. Generally, the nickel contained in zinc-nickel alloys is approximately
If it exceeds 17wt%, the subsequent chromate treatment will be adversely affected. Furthermore, if the amount of nickel in the electroplated film exceeds 25 wt%, the film will darken and have a poor appearance, and the chromate treatment of such a blackened film will not be carried out well, resulting in poor corrosion resistance. An object of the present invention is to solve these problems in conventional zinc-nickel alloy electroplating. Means for Solving the Problem The above object is to produce a chloride type and chloride-sulfate mixture containing sufficient amounts of zinc and nickel ions to electrodeposit a zinc-nickel alloy of the desired alloy composition. type of aqueous acidic zinc-nickel alloy electroplating solution according to the present invention. The plating solution may further contain a polyoxyalkylene compound or a terminal-substituted derivative thereof soluble in the bath in an amount effective for forming fine particles in the electroplated film. In addition, this plating solution contains (a) an aromatic sulfonic acid represented by the general formula () (b) aromatic sulfonamide, sulfonimide, and mixed carbonamide/sulfonamide (c) acetylene alcohol (a and b). contains any of the additives selected from the group consisting of salts thereof which are soluble and compatible with the bath, as well as mixtures thereof. Additives (a), (b) and (c) are chloride type and chloride-sulfuric acid in amounts effective to suppress nickel eutectoid in the low current section and provide a substantially uniform alloy composition. Added to salt-mixed plating solutions. The uniformity of the alloy film composition from chloride type and chloride-sulfate mixed type plating solutions can be improved by using additives (a), (b) and (c) at an additive concentration of approximately 0.001 mol. / or more is acceptable. In addition to the above composition, the plating solution of the present invention may also contain secondary brighteners and auxiliary brighteners that are effective in electrodepositing zinc-nickel alloy coatings having a decorative, glossy appearance. Further, in order to stabilize the pH of the plating solution in the range of about 0 to approximately neutral, preferably in the range of about 2 to 6, a well-known buffering agent may be included. Hereinafter, the plating solution according to the present invention will be explained in more detail. The aqueous acidic zinc/nickel alloy electroplating solution according to the present invention consists of an aqueous solution containing an effective amount of zinc ions for zinc electrodeposition, and the concentration is usually 10 g/
to saturation, more commonly around 15-225g/
It is. In most cases, the zinc ion concentration is around 20
It is adjusted to a range of ~200g/. The maximum concentration of zinc ions varies depending on the temperature of the plating solution, and the higher the temperature, the higher the concentration can be adopted. Zinc ions are introduced into the plating solution in the form of a soluble zinc salt, such as chloride or sulfate, along with an acid appropriate to the type of zinc salt used, such as hydrochloric acid or sulfuric acid. Usually, zinc/nickel alloy electroplating solution is used.
The PH is adjusted to a range of about 0-7, with a preferred PH of 2.
~6. The plating solution of the present invention contains a certain amount of nickel ions as well as zinc ions. Like zinc ions, nickel ions are available in the form of bath-soluble salts such as chlorides and sulfates, depending on whether the plating solution is a chloride type or a mixed chloride-sulfate type. introduced into the soaking liquid. In order to obtain a zinc-nickel alloy film containing about 0.1 to about 30% by weight of nickel, the nickel ion concentration is usually kept at about
0.5g/~120g/. The preferred nickel content of the zinc-nickel alloy coating is about 3 to about 15
Weight%. For decorative zinc-nickel alloy coatings, it is desirable to keep the weight ratio of zinc ions to nickel ions in the plating solution lower than about 2.5. To replenish zinc and nickel ions while using a zinc-nickel alloy electroplating solution, use a zinc metal anode, a nickel metal anode, or a zinc-nickel alloy anode that gradually dissolves into the plating solution during electrolysis. . Concentration adjustment during work can also be carried out by supplementing the zinc salt and nickel salt in the plating solution preparation bath. The zinc-nickel alloy electroplating solution of the present invention is
In addition to zinc and nickel ions, it contains additives selected from the following group: (a) aromatic sulfonic acids of the general formula and mixtures thereof; In the formula, M is H, _NH4 , or group A and group A metal, zinc or nickel; X is H, alkyl having 1 to 4 carbon atoms, 1 carbon number
~6 hydroxyalkyl, aryl having 6 to 10 carbon atoms, arylalkyl having 7 to 10 carbon atoms, halogen, polyalkylaryl that is soluble in bath (however, the number of carbon atoms in the alkyl group is 1 to 4),
SO ₃ M, or CHO; provided that the aryl substituent may be an adjacent cyclic compound; Y is H, alkyl having 1 to 4 carbon atoms, SO ₃ M, or halogen. (b) aromatic sulfonamides, sulfonimides and mixed carbonamides/sulfonamides and mixtures thereof of the general formula;

[expression] and In the formula, X is H, alkyl having 1 to 6 carbon atoms, 6 carbon atoms
~10 aryl (which may be adjacent to the phenyl ring), alkylaryl having 7 to 22 carbon atoms,
OH, halogen, CHO, alkoxy having 1 to 4 carbon atoms, carboxy having 1 to 6 carbon atoms, 1 to 6 carbon atoms
6 hydroxyalkyl, or 1 to 6 carbon atoms
sulfoalkyl; Y is H, alkyl having 1 to 6 carbon atoms, OH,
SO ₃ M, or phenyl; Q is H, M, alkyl having 1 to 3 carbon atoms, sulfoalkyl having 1 to 6 carbon atoms, hydroxyalkyl having 1 to 6 carbon atoms, alkoxysulfo having 1 to 4 carbon atoms; M is H, NH ₄ , zinc, nickel or A
group and group metals; Z is H, Q,

【formula】

[Formula] (c) Acetylene alcohol of general formula; General formula In the formula, m is an integer of 0 to 4; n is an integer of 1 to 4; R ₁ is H or carbon number 1 to 6 when m is 0;
alkyl, when m is greater than 0 -O-
R ₄ ; R ₂ and R ₃ are H, alkyl or sulfoalkyl having 1 to 4 carbon atoms; R ₄ is H or

[Formula] p is an integer of 1 to 4; R ₅ is H or alkyl having 1 to 2 carbon atoms. The above (a) and (b) include salts thereof that are soluble and compatible with the bath, and mixtures thereof. The following table shows typical additives that can be used. Table 1 Additives (a) Aromatic sulfonic acids (1) Sodium benzenesulfonate (2) Sodium 1-naphthalenesulfonate (b) Aromatic sulfonamides, sulfonimides and mixed carboxamides/sulfonamides (3) Benzenesulfonamides (4) Satucarin sodium (c) Acetylene alcohol (5) 3-methyl 1-butyn-3-al (6) HC≡CC (CH ₃ ) ₂ O (CH ₂ CH ₂ O) ₂ H (3-methyl 1 -butyne-3-al ethylene oxide adduct) (7) Butynediol (8) HOCH ₂ CH ₂ OCH ₂ C≡CCH ₂ OCH ₂ CH ₂ OH (butynediol ethylene oxide adduct) (9) HOCH ₂ C ≡CCH ₂ OCH ₂ CH ₂ OH (10) Propargyl alcohol (11) HC≡CCH _{2 OCH 2} CH ₂ OH (ethylene oxide adduct of propargyl alcohol) (12) HC≡CCH ₂ OCH ₂ CH (CH ₃ ) OH ( (Propylene oxide adduct of propargyl alcohol) (13) Hexinediol In order to understand the performance of the additive in the comparative tests shown in Examples 9 to 21 below, the individual compounds shown in Table 1 above are numbered. Group (a) additives include (1)
And as a typical example other than (2), the number of carbon atoms is 1~
Acids and their salts which are derivatives of benzene and naphthalene substituted with 4 alkyl groups, such as benzenesulfonic acid (mono, di, and tri), p-
Bromobenzenesulfonic acid, benzaldehyde sulfonic acid (o, m, p), diphenylsulfonesulfonic acid, naphthalenesulfonic acid (mono, di, and tri), benzenesulfohydroxamic acid,
Examples include p-chlorobenzenesulfonic acid, diphenylsulfonic acid, dichlorobenzenesulfonic acid, 3-phenyl-2-propyne-1-sulfonic acid, and others. In addition to (3) and (4) in Table 1, group (b) additives include m-benzenesulfonamide, N-substituted sulfopropyl saccharin, o
-benzoic acid sulfimide, benzenedisulfonamide, toluenesulfonamide (o, p), naphthalenesulfonamide (alpha, beta), N
-(2-hydroxypropyl-3-sulfonic acid)-
N-phenylsulfonylbenzamide, N-benzoylbenzenesulfimide, p-toluenesulfochloramide, p-bromobenzenesulfonamide, p-benzoic acid sulfonamide, benzoic acid sulfone dichloramide (o,p), p-toluene Sulfone chloramide, p,p'-diphenyldisulfonamide, benzene m-disulfonamide, 6
-Chloro-o-benzoylsulfonimide, m-
Formylbenzenesulfonamide, sulfomethylbenzenesulfonamide, benzenesulfonamide m-carboxamide, 7-formyl-o-
Benzoylsulfimide, N-acetylbenzenesulfonimide, methoxybenzenesulfonamide, hydroxymethylbenzenesulfonamide,
p-carbonamide benzenesulfonamide, p
-Chlorobenzenesulfonamide, N-sulfoethylsaccharin. The compounds of groups (b) and (c) are also effective in improving the ductility of electroplated coatings, thereby virtually eliminating minute cracks in the electroplated coatings on substrates such as steel. It is known to improve corrosion resistance. For this purpose, the compounds of groups (b) and (c) have been observed to be effective at concentrations as low as about 0.0001 mol/mol. Although concentrations as high as 0.1 mol/mole/mole/mole/mole/mole/mole/mole/mole/mole/mole/mole/mole/mole/mole/mole/mole concentration range may be as high as 0.1 mol/m. is desirable. In addition, the compounds of each group (a), (b), and (c) and mixtures thereof are usually about 0.001 to about 0.1 in chloride type and chloride-sulfate mixed type plating solutions.
Concentrations of at least about 0.01 mole/mole/mole/mole/mole/mole/mole/mole/molar have been found to be effective in producing more uniform alloy electroplated coatings over a wide range of cathodic current densities. In conventional zinc-nickel alloy electroplating solutions, when complex parts are plated, the nickel concentration increases in the low current density areas compared to the nickel content of the alloy film in the high current density areas. By using the additive of the present invention, nickel co-deposition in low current density areas is suppressed, and the amount of nickel in the alloy coating becomes substantially uniform over the entire surface of the plating. The additives have also been found to improve the cathode efficiency of the low current section, thereby increasing the uniformity of the bath and improving the corrosion resistance of the plated parts. Although this improvement is achieved in chloride-type and mixed chloride-sulfate-type plating solutions, improved ductility is also achieved when these additives are used in sulfate-type plating solutions. However, it is not very effective in suppressing nickel eutectoid formation in the low current section. In addition to the above-mentioned essential components, the plating solution of the present invention contains a polyoxyalkylene compound as a carrier brightening agent, which makes the particles of the zinc-nickel alloy electroplated film fine and gives at least semi-gloss in the absence of an auxiliary brightening agent. It may be present in an amount sufficient to obtain an external plating film, which is particularly desirable in the case of chloride-containing plating solutions. For this purpose, the polyoxyalkylene compound can be used in a trace amount of about 0.005 g/ to a saturation amount, but preferably in a concentration of about 0.1 to 200 g/. Typically, the concentration of the polyoxyalkylene compound ranges from about 0.02 to about 20 g/g, with concentrations of about 0.02 to about 5 g/g being desirable in many applications. The polyoxyalkylene compound is not limited to nonionic compounds, but may be ionic compounds. Furthermore, it may consist of a terminally substituted derivative soluble in a plating solution or a mixture thereof. Representative nonionic polyoxyalkylene compounds that can be used in the practice of the present invention include condensation copolymers of one or more alkylene oxides (having 1 to 4 carbon atoms) and other compounds (including the other compounds mentioned above). from about 10 to about 70 moles of alkylene oxide per mole). Examples of the above other compounds (which may be alkoxylated) include straight chain alcohols,
aliphatic monohydric alcohol, aliphatic polyhydric alcohol,
Alcohols such as acetylene mono- or polyols and phenolic alcohols; fatty acids; aliphatic amides; alkylphenols; alkylnaphthols;
Examples include aliphatic amines (either monoamines or polyamines). Representative examples of preferred polyoxyalkylene compounds of this type include the following. A Nonionic copolymer of alkylene oxide and linear alcohol having the following structural formula: In the formula, x is an integer of 9 to 15, and n is an integer of 10 to 50. B Nonionic copolymer of alkylene oxide and phenol alcohol having the following structural _formula : H-( _CH2 )x-Ar-O-( _CH2CH2O ) _nCH2CH2OH In _the formula, Ar is Benzene ring, x is an integer from 6 to 15,
n is an integer from 10 to 50. C A nonionic homopolymer of alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide, glycidol, butylene oxide and mixtures thereof. D Specific examples of nonionic polyoxyalkylene compounds that can be used in the present invention include alkylphenols (e.g. nonylphenol),
Alkylnaphthol, aliphatic monohydric alcohol,
There are alkoxylated products of hexynediol and decinediol, ethylenediamine, tetraethanol, fatty acids, aliphatic alkanolamides (eg, amides of coconut fatty acids), or esters (eg, sorbitan monopalmitate). In place of the nonionic polyoxyalkylene compounds mentioned above, bath-soluble terminally substituted polyoxyalkylene compounds, namely (1) alkylenes selected from the group consisting of ethylene oxide, propylene oxide, glycidol, butylene oxide and mixtures thereof; Sulfation, amination, phosphoric acid treatment of oxide polymer; and (2) alkoxylation of mono- and polyhydroxy compounds selected from the group consisting of alkyl, alkenyl, alkynyl, aryl and mixtures thereof having a hydroxyl group; Chlorination, bromination, phosphonation, sulfonation, carboxylation,
And those obtained by a combination of these can also be used. The molecular weight of the polyoxyalkylene compound is adjusted so that the additive can be dissolved in the plating solution at a desired concentration. In addition, terminally substituted compounds are
Depending on the degree of substitution and the number of reactive hydroxyl groups in the molecule, the molecule may have one terminal substituent or two or more terminal substituents. Other polymeric carrier brighteners may be included in the zinc-nickel alloy electroplating solutions of the present invention in conjunction with, or in place of, the polyoxyalkylene carrier brighteners described above. A polymeric carrier brightener that can be used is U.S. Pat. No. 4,401,526.
No. 4,425,198 and No. 4,488,942, the teachings of which are hereby incorporated by reference. In addition to the above-mentioned components, the plating solution of the present invention also contains:
Contains auxiliary additives such as buffers and bath modifiers (e.g. boric acid, acetic acid, citric acid, benzoic acid, salicylic acid, bath-soluble and compatible salts of these acids) as required. can be done.
Furthermore, in order to increase the conductivity of the plating solution, a conductive salt can be included, and the appropriate concentration is approximately
20 to about 450g/. Conductive salts that can be used in this case are typically alkali metal salts and ammonium salts in the form of chlorides or sulfates, depending on the type of plating solution used.
Specific examples thereof include ammonium sulfate, ammonium chloride, ammonium bromide, magnesium sulfate, sodium sulfate, potassium sulfate, sodium chloride, and potassium chloride. For chloride type and chloride-sulfate mixed type plating solutions,
It is desirable that the plating solution contains about 20 g or more of ammonium ions. The zinc-nickel alloy electroplating solution containing the above-mentioned essential components provides a plated film with a semi-gloss appearance. A semi-gloss appearance is usually sufficient for functional or industrial plating coatings. When decorative plating with a complete gloss or mirror appearance is required, it is desirable to also include a secondary brightener and/or an auxiliary brightener in the plating solution. The secondary brightener can be added in an amount sufficient to impart a specular gloss to the plated coating up to its maximum solubility in the bath. Desirably, the plating solution contains about 0.01 to about 2 g of these secondary brighteners. Representative examples of aromatic aldehydes or ketones that can be used as secondary brighteners include aryl aldehydes and aryl ketones, ring-halogenated aryl aldehydes and aryl ketones, and heterocyclic aldehydes and ketones. Specific examples of those that can be used include o-chlorobenzaldehyde, p-chlorobenzaldehyde, benzyl methyl ketone, phenylethyl ketone, cinnamaldehyde, benzalacetone, thiophenaldehyde, furfural-5-hydroxymethylfurfural, and furfurylidene acetone. , furfuraldehyde, 4-(2-furur)-3-buten-2-one, and the like. The plating solution of the present invention may contain an auxiliary brightener for the low current density portion, regardless of whether or not the above-mentioned secondary brightener is used. Suitable auxiliary brighteners are lower alkyl carboxylic acids having alkyl groups of about 1 to about 6 carbon atoms and bath-soluble salts thereof. Although both the acid itself and its bath-soluble salts can be used, the sodium, potassium or ammonium salts are often preferred. A particularly preferred auxiliary brightener in the present invention is sodium acetate. Typically, auxiliary brighteners are used in amounts ranging from about 0.5 to about 20 g/g, with about 1 to 10 g/g being particularly preferred. When the plating solution of the present invention is used at the upper end of the pH range, for example from about 7 to about 8, it may be better to include a suitable complexing agent in the bath to prevent precipitation of zinc and/or nickel. be. Zinc and/or
Any complexing agent suitable for nickel or nickel can be used in an amount sufficient to prevent precipitation of zinc and/or nickel from the bath.
Typical examples of complexing agents that can be used are ethylenediaminetetraacetic acid, diethylenetetraminepentaacetic acid and
Quadrol (N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine). The zinc-nickel alloy electroplating of the present invention is performed by depositing zinc on a conductive substrate at temperatures ranging from room temperature (15°C) to about 82°C, typically from about 21°C to about 60°C.
Used for electroplating nickel alloys. Electroplating of zinc/nickel alloy is approximately 0.1 to approx.
It is carried out at an average cathodic current density of 220 A/dm ² or more. Decorative chloride types and chloride-
For sulfate mixed type plating solutions, it is usually desirable to have a current density of about 0.1 to about 9 A/ ^dm2 , while for mechanical chloride type plating solutions, the average cathode current density should be about ² to 220A/dm2. During plating, it is desirable to agitate the bath or plating solution mechanically, by circulating the solution, or by moving the workpiece. The plating solution of the present invention can be used for both rack and barrel plating. When zinc and nickel are used as anodes, the surface area ratio of the anodes can be varied in order to replace the desired amount of zinc and nickel ions contained in the plating solution being used. Generally, a zinc anode to nickel anode surface area ratio of about 9 to 1 has been found to be effective in maintaining a desirable concentration of zinc and nickel ions in the plating solution. Effects of the Invention According to the present invention, an undesirable increase in the nickel eutectoid rate in a low current density area is suppressed, and not only the problem of blackening of plating but also the problem of difficulty in chromate treatment is solved. At the same time, the cathode efficiency in the low current density area is improved, resulting in better plating coverage, and when additives (b) or (c) are used, the ductility of the plating film is also improved.
A plated film with good corrosion resistance can be obtained. As a result of these effects, the present invention provides zinc that is superior in various properties such as color tone, gloss, ductility, and corrosion resistance compared to conventional ones, regardless of the shape of the object to be plated or the plating method used. -It becomes possible to perform nickel alloy electroplating. Examples In order to further explain the plating liquid composition of the present invention and the plating method using the same, examples are shown below.
However, this is merely an example and is not intended to limit the scope of the invention as described above. Example 1 Zinc chloride 100g/, nickel chloride hexahydrate 130g
g/, ammonium chloride 200 g/, sodium acetate 8 g/ as a buffer, polyoxyalkylene compound (2,4,7,9-tetramethyl-5-decyne-4,7 ethoxylated with 30 mol of ethylene oxide) A chloride-type zinc-nickel alloy electroplating solution containing 5 g/diol) and 0.05 g/benzalacetone and having a pH adjusted to 5.3 with ammonium hydroxide was prepared. Steel J-panels were plated at an average current density of 2.7 A/dm ² and a liquid temperature of about 34°C. The obtained zinc-nickel alloy film was completely glossy and contained 9.7 wt% nickel, but after one week, microcracks appeared in the film and the ductility of the film was unstable. It was shown that An additive of 0.5 g/saccharin sodium was added to the above plating solution, and a J-panel was plated under the same conditions. The resulting zinc-nickel alloy film was completely glossy and also had a nickel content of about 9.7 wt%. The alloy film was highly ductile and remained free of microcracks. Examples 2 to 14 100g/zinc chloride as basic ingredients, 130g/
of nickel chloride hexahydrate, 200 g/ammonium chloride, 4 g/ammonium acetate, 5
g/g of polyoxyalkylene compound (2, ethoxylated with 30 mol of ethylene oxide)
4,7,9-tetramethyl-5-decyne-4,9
An aqueous acidic zinc/nickel alloy electroplating solution containing 0.1 g/second brightener/benzylidene acetone was prepared. The pH of this plating solution
5.7 and the temperature was controlled at approximately 35°C. Steel hull test panels were plated using a Hull cell at 2 amps of current for 5 minutes without stirring. Additives (1) to (13) as shown in Table 1
The above test was repeated in the same manner except that 0.015 mol/ was added. A colorless, beautiful mirror-glossy film was formed on all 13 test panels plated using each additive. In contrast, test panels plated using a plating solution without additives had a dark film along the low current density areas. Table 2 summarizes how effective the additive was in suppressing nickel eutectoid formation in the low current density area, in comparison with the case of a plating solution without additives. In Table 2, the same symbols as in Table 1 above are given to additives.

[Table] From the results shown in Table 2 in comparison with the control example, it is clear that when additives (1) to (13) are used, the nickel in the low current area (especially in the 0.5A/ ^dm2 region) is lower than the control example. It can be seen that the eutectoid is significantly reduced. It is also clear that the use of additives significantly increases cathode efficiency. It is clear that the preferred embodiments of the present invention disclosed above fully achieve the objects of the present invention described above, but the present invention may be modified in various ways without departing from the scope of the claims. It goes without saying that you can get it.

Claims (1)

[Claims] 1. Contains sufficient amounts of zinc ions and nickel ions to electrodeposit a zinc-nickel alloy,
As an additive in chloride type or chloride-sulfate mixed type aqueous electroplating solutions for electroplating zinc/nickel alloys on substrates,
one or more compounds selected from the group consisting of (a), (b) and (c) below in an amount effective to suppress nickel eutectoid in the low current section and provide a substantially uniform alloy composition; A zinc-nickel alloy electroplating solution characterized by containing: (a) aromatic sulfonic acid represented by the following general formula: where M is H, NH ₄ or a group A and A metal, zinc or nickel;
Alkyl having 1 to 4 carbon atoms, hydroxyalkyl having 1 to 4 carbon atoms, aryl having 6 to 10 carbon atoms, arylalkyl having 7 to 10 carbon atoms (however, the number of carbon atoms in the alkyl group is 1 to 4), halogen,
Bath-soluble polyalkylaryl, SO ₃ M, or CHO, provided that the aryl substituent may be a vicinal cyclic compound; Y is H, 1 carbon number
-4 represents alkyl, _SO3M or halogen; (b) aromatic sulfonamides, sulfonimides and mixed carbonamides/sulfonamides (c) acetylene alcohols. 2. The plating solution according to claim 1, wherein the zinc ion content is from about 10 g/ to saturation. 3. The plating solution according to claim 1, wherein the zinc ion content is about 15 to about 225 g/. 4. The plating solution according to claim 1, having a zinc ion content of about 20 to about 200 g/. 5 Nickel ion content is approximately 0.5 to approximately 120g/
A plating liquid according to claim 1. 6 Zinc ion content and nickel ion content are about 3% to about 15% by weight of nickel.
The plating solution according to claim 1, which is in an amount that provides electroplating of nickel alloy. 7. A plating solution according to claim 1, which contains a carrier brightener in an amount effective to refine the particles of the electroplated coating. 8 The content of additives (b) and (c) is approximately 0.0001 mol/
The plating liquid according to claim 1, which is as follows. 9 The content of additives (b) and (c) is about 0.001 to about
The plating solution according to claim 8, wherein the plating solution is 0.01 mol/. 10 The content of additives (a), (b) and (c) is approximately 0.001
The plating solution according to claim 1, wherein the plating solution is about 0.1 mol/min. 11. The plating solution according to claim 10, wherein the content of additives (a), (b) and (c) is about 0.01 mol/or more. 12 Carrier brightener content is approximately 0.005g/
8. The plating solution according to claim 7, comprising a polyoxyalkylene compound ranging from saturated to saturated. 13 Carrier brightener content is about 0.1 to about 200
8. The plating solution according to claim 7, which comprises a polyoxyalkylene compound in an amount of 14 Carrier brightener content is approximately 0.001g/
The plating solution according to claim 7, which comprises a polyacrylamide compound and its N-substituted derivative up to the solubility limit in the plating solution. 15 Carrier brightener content is about 0.1 to about 5
g/ of polyacrylamide compound and its N
- The plating liquid according to claim 7, which comprises a substituted derivative. 16. The plating solution according to claim 1, which contains hydrogen ions that adjust the pH from about 0 to neutral. 17. The plating solution according to claim 1, which contains hydrogen ions that adjust the pH to about 2 to about 6. 18. The plating solution according to claim 1, which contains a buffering agent. 19. The plating solution according to claim 1, which contains an effective amount of a secondary brightener to impart gloss to the electroplated film. 20. The plating solution according to claim 1, containing about 0.01 to about 2 g/secondary brightener. 21. The plating solution according to claim 1, which contains an auxiliary brightener in an amount effective to impart gloss to the electroplated film in the low current density region. 22. The plating solution according to claim 21, wherein the content of the auxiliary brightener is about 0.5 to about 20 g/. 23. The plating solution according to claim 21, wherein the content of the auxiliary brightener is about 1 to about 10 g/g/. 24 Conductive salts that are soluble and coexist with plating solution
A plating solution according to claim 1 containing up to 450 g/ml. 25. The plating solution according to claim 1, containing about 20 g/or more of ammonium ions. 26. The plating solution of claim 1, which contains a complexing agent in an amount sufficient to maintain an effective amount of zinc ions and nickel ions in the solution. 27. The plating solution according to claim 1, wherein the additive (b) consists of a compound represented by the following general formula, a salt of the compound that is soluble and compatible with the bath, and a mixture thereof: General formula and In the formula, X is H, alkyl having 1 to 6 carbon atoms, aryl having 6 to 10 carbon atoms (may be adjacent to the phenyl ring), alkylaryl having 7 to 22 carbon atoms,
OH, halogen, CHO, alkoxy having 1 to 4 carbon atoms, carboxy having 1 to 6 carbon atoms, hydroxyalkyl having 1 to 6 carbon atoms, or sulfoalkyl having 1 to 6 carbon atoms; Y is H, alkyl,
OH, SO ₃ M, or phenyl; Q is H, alkyl having 1 to 3 carbon atoms, sulfoalkyl having 1 to 6 carbon atoms, hydroxyalkyl having 1 to 6 carbon atoms, alkoxysulfo having 1 to 4 carbon atoms; M is H, NH ₄ , zinc, nickel or group A and group metals; Z
is H, Q, [Formula] [Formula] 28 The plating liquid according to claim 1, wherein the additive (c) consists of a compound represented by the following general formula: General formula In the formula, m is an integer of 0 to 4; n is an integer of 1 to 4; R ₁ is H or alkyl having 1 to 6 carbon atoms when m is 0; -O-R ₄ when m is larger than 0; R ₂ and R ₃ are H, alkyl having 1 to 4 carbon atoms, or sulfoalkyl; R ₄ is H or [Formula] p is an integer of 1 to 4; R ₅ is H or alkyl having 1 to 2 carbon atoms; 29. The plating solution according to claim 1, wherein the additive (c) is a compound selected from the following compound group: 3-methyl-1-butyn-3-al 3-methyl-1-butyn-3 HC≡CC(CH ₃ ) ₂ O(CH ₂ CH ₂ O) ₂ H which is an ethylene oxide adduct of −R; Butynediol; HOCH ₂ CH ₂ OCH ₂ C≡CCH ₂ which is an ethylene oxide adduct of butynediol OCH ₂ CH ₂ OH; HOCH ₂ C≡CCH ₂ OCH ₂ CH ₂ OH; Propargyl alcohol; HC≡CCH ₂ OCH ₂ CH ₂ OH, which is an ethylene oxide adduct of propargyl alcohol; HC, which is a propylene oxide adduct of propargyl alcohol ≡CCH ₂ OCH ₂ CH (CH ₃ )
OH; hexynediol; and mixtures thereof.